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Toxics · 2025 ·Vol. 13 ·期 6 ·427 · IF 4.1

Chronic Low-Dose Phoxim Exposure Impairs Silk Production in Bombyx mori L. (Lepidoptera: Bombycidae) by Disrupting Juvenile Hormone Signaling-Mediated Fibroin Synthesis

Xinyi Xie,Jiayin Hou,Meng Li,Zhiyu Liu,Mengai He,Chenxi Li,Xiaohua Du,Liezhong Chen

Phoxim is a pesticide extensively applied in mulberry fields, and residues may persist on leaves even after the recommended pre-harvest interval. However, the potential risks of these residues toBombyx moriL. (Lepidoptera: Bombycidae) have long been overlooked. The results demonstrated that chronic low-dose exposure from the second to fifth instars significantly impaired silkworm development and silk production. Specifically, larvae in the 0.316 μg/mL treatment group (1/2 LC50) exhibited a significant reduction in body weight, while the cocoon shell ratio was significantly decreased in both the 0.079 μg/mL (1/8 LC50) and 1/2 LC50groups. Cocoon deformities were observed in the 0.032 μg/mL (1/20 LC50), 1/8 LC50, and 1/2 LC50groups. Histopathological analysis revealed silk gland damage in the treatment groups, with severity increasing with higher phoxim concentrations. Biochemical analyses indicated elevated malondialdehyde (MDA) levels accompanied by increased superoxide dismutase (SOD) and peroxidase (POD) activities. Notably, phoxim exposure selectively reduced juvenile hormone (JH) titers without affecting ecdysone titers. JH-regulated genes including the receptorsMet1andMet2, and transcription factorsKr-h1andDimmwere downregulated, accompanied by suppressed expression of the fibroin synthesis geneFib-H. These results collectively indicate that chronic low-concentration phoxim exposure disrupts endocrine regulation, damages silk gland integrity, and ultimately reduces silk production in silkworm.

CAS / MDL: 14816-18-3
研究领域: 昆虫学 · 毒理学 · 分子生物学 · 内分泌学 · 农业科学
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Journal of Food Measurement and Characterization · 2024 ·Vol. 18 ·期 5 ·3344-3352 · IF 2.9

Wool keratin-based colorimetric detection of organophosphorus pesticides via a multi-enzyme cascade reaction

Cao Mengrui,Xu Yiwei,Jia Xupeng,He Baoshan,Ren Wenjie,Wei Min,Suo Zhiguang,Jin Huali,Zhao Wenhong

A simple and sensitive colorimetric method for organophosphorus pesticides (Ops) detection was proposed via a multi-enzyme cascade reaction. The coordination compound of wool keratin and Cu (WK-Cu) was synthesized by self-assembly and used as a key catalyst in the cascade reaction. The enzymatic kinetics curve was established to explore the catalytic property, and the obtained K m and V max proved that WK-Cu has a good peroxidase-like activity. Ops could inhibit acetylcholinesterase activity and trigger the multienzyme cascades process, resulting in an amplified response signal. The key conditions were optimized, such as enzyme-linked reaction time and the concentration of each reactant in Ops detection. The detection range of phoxim was 10-1000 µg/L with a detection limit of 2.31 µg/L. Compared with other colorimetric detections, the proposed method exhibited a wider detection range and a relatively lower detection limit. In addition, this colorimetric method showed good universality and anti-interference ability for the analysis of phoxim in apple, cabbage and cauliflower samples. Owing to these merits, the proposed method has a good application prospect in Ops detection.

研究领域: 分析化学 · 环境科学 · 生物化学 · 酶学 · 材料科学
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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

Ion Luminescent Micelles: A Surfactant-Mediated Double-End Signal Amplification Strategy for Portable Detection of Phoxim

Siying Che,Gaoqiong Deng,Yaoyu Qi,Xiutan Peng,Haiyan Fu,Yuanbin She

Residues of organophosphorus pesticides (OPs) raise considerable concern, while achieving high enough detection sensitivity is still a challenge for on-site fluorescence techniques. Herein, we report a “double-end samplification” strategy by encapsulating a low-emission fluorescent ion probe [DCF][P66614]2 into a cetyltrimethylammonium bromide (CTAB) hydrophobic core to form ionic luminescent micelles. At the probe end, ionic liquid micelles locally concentrated the probes, achieving a 350-fold fluorescence enhancement. Benefiting from the strong fluorescence characteristics of DCFP@CTAB, the electron transfer effect between phoxim and DCFP@CTAB, and the fluorescence “turn-off” caused by phoxim, fluorometric and colorimetric methods for simple and sensitive determination of phoxim were proposed. At the analyte end, electrostatic interactions and hydrophobic micellar cavities enhanced phoxim adsorption, improving the fluorescence quenching efficiency by 149%. Under optimized experimental conditions, this sensing platform with a “turn-off” pattern achieves visual limits of detection of 1.7 × 10–7 M and 3.0 × 10–8 M for colorimetric and fluorescence patterns, respectively. Besides, to meet the demand for convenient detection of phoxim, a self-correcting portable paper-based device was constructed, which enabled on-site quantitative analysis of phoxim with a LOD of 0.3 μM. This work represents the first attempt to assemble an ionic liquid with a surfactant, effectively improving the sensitive detection of trace pesticide residues and providing a method for on-the-spot monitoring of food safety.

研究领域: 分析化学 · 环境监测 · 食品安全 · 荧光传感器 · 纳米技术 · 农药残留检测
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Anchoring biomimetic Zn site in metal–organic framework nanozyme to enhance phosphatase-like catalytic activity for discrimination of organophosphorus pesticides

Yusha Huang,Longcheng Gong,Chengli Xie,Wenling Qin,Min Wang,Lianzhe Hu,Zhining Xia

Herein, a biomimetic approach is developed to improve the phosphatase-like catalytic activity of a metal–organic framework (MOF) nanozyme. Specifically, biomimetic Zn sites, featuring a coordination environment similar to that of natural phosphatase, were covalently anchored into UiO-66-NH 2 nanozyme through a step-by-step modification process. Compared with pristine UiO-66-NH 2 , the resultant 66-IS-Zn exhibited a 130-fold increase in K cat . Mechanism studies suggest that the anchoring of Zn sites can only enhance the catalytic performance of MOFs that possess intrinsic phosphatase-like activity, and the enhancement of catalytic activity strongly relies on the coordination environment of Zn sites, which involves the co-coordination of N and O with Zn. Besides the excellent phosphatase-like activity, 66-IS-Zn also exhibited enhanced intrinsic fluorescence emission and high phosphodiesterase-like catalytic activity. Consequently, 66-IS-Zn was used as the sensing unit to construct a three-channel sensor array for distinguishing organophosphorus pesticides (OPs). This sensor array can successfully distinguish six OPs and allow the quantification of profenofos and phoxim. Moreover, the binary mixtures of OPs and cherry tomato samples were precisely discriminated without any overlapping, indicating the reliability and practicability of the sensor array.

研究领域: 生物化学 · 材料科学 · 分析化学
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JOURNAL OF CHROMATOGRAPHY A · 2025 · IF 4

The adsorption determination of organophosphate pesticides on microplastics in aquatic and juice samples using a Zr-COF-based magnetic solid-phase extraction

Yufei Liu,Sitian Gu,Wenli Zhu,Man Gong,Qingli Yang,Xiudan Hou

In order to study the adsorption interaction and behavior of organophosphate pesticides (OPPs) on the surface of different microplastics, a Zr-covalent organic framework (COF)-based magnetic solid-phase extraction (MSPE) was established. Due to various interactions (π-π interaction, hydrogen bonding and Zr-O-P coordination interactions), Zr-COF exhibited higher adsorption capacities towards five OPPs than COF without Zr through the theoretical calculation and analysis. The established MSPE-HPLC method showed the detection limit of 0.011–0.019 mg L −1 for OPPs. It was used to determine the adsorption performance of four microplastics towards OPPs. Small sized and aging microplastics showed more adsorption capacities than the large sized and original microplastics. Polylactic acid exhibited higher adsorption capacities than most OPPs, especially with the N element, -NO 2 , and P=O groups, due to the presence of hydrogen bonding. Besides, the method matrix effect was between 2.90%-17.84% in real samples, and the adsorption capacity in juice was significantly higher than that in aquatic samples because of the acidic environment.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Mn-modified porphyrin metal–organic framework mediated colorimetric and photothermal dual-channel probe for sensitive detection of organophosphorus pesticides

Zheng Wang,Hui Li,Chuang Jiang,Wenya Liu,Siyu Zhang,Yibin Zhou,Kang Liu,Yaqing Xiao,Ruyan Hou,Xiaochun Wan,Yingnan Liu

Herein, a novel dual-mode probe for organophosphorus pesticides (OPs) colorimetric and photothermal detection was developed based on manganese modified porphyrin metal–organic framework (PCN-224-Mn). PCN-224-Mn had excellent oxidase-like activity and oxidized colorless 3,3,5,5-tetramethylbenzidine (TMB) to blue–green oxidation state TMB (oxTMB), which exhibited high temperature under near-infrared irradiation. l -ascorbate-2-phosphate was hydrolyzed by acid phosphatase to produce ascorbic acid, which weakened colorimetric and photothermal signals by impacting oxTMB generation. The presence of OPs blocked the production of ascorbic acid by irreversibly inhibiting the activity of acid phosphatase, causing the restoration of chromogenic reaction and the increase of temperature. Under the optimal conditions, the probe showed a good linear response to OPs in the concentration range of 5 ∼ 10000 ng/mL, using glyphosate as the analog. The detection limits of glyphosate in colorimetric mode and photothermal mode were 1.47 ng/mL and 2.00 ng/mL, respectively. The probe was successfully used for sensitive identification of OPs residues in tea, brown rice, and wheat flour. This work proposes a simple and reliable colorimetric/photothermal platform for OPs identification, which overcomes the problem that single-mode detection probes are susceptible to external factors, and has broad application potential in the field of food safety.

研究领域: 分析化学 · 环境科学 · 食品科学
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Nature Communications · 2025 ·Vol. 16 ·期 1 ·1-14 · IF 15.7

Pickering emulsions with low interface coverage but enhanced stability for emulsion interface catalysis and SERS-based detection

Li Mingkun,Song Qing,Wang Yilin,Liu Bing

Particle adsorption at the oil-water interface is an important strategy for emulsion stabilization against coalescence, however, the particle occupation of the interface and the requirement of free interfaces in many applications is a contradiction. We report an emulsion type with low droplet surface coverage but enhanced stability by employing colloidal rings as emulsifiers. The formed emulsions provide a large accessible oil-water interface (>80%). The enhanced diffusion through the interface and highly efficient loading of catalytic nanoparticles at the interface result in much higher catalytic efficiency than the nanosphere-covered emulsions in both batch and continuous flow interface catalysis. The loading of plasmonic nanoparticles brings excellent performance in surface-enhanced Raman spectroscopy-based detection, which exhibits the lowest detectable concentration as low as 10 −11  M using only 0.25 μL of analyte and 0.2 μg of Au nanoparticles. The ring-based Pickering emulsion provides freedom for designing interface structures and compositions for functional emulsions.

研究领域: 化学工程 · 纳米技术 · 分析化学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Smartphone-based colorimetric paper chip sensor using single-atom nanozyme for the detection of carbofuran pesticide residues in vegetables

Lifan Zhang,Ziyue Lang,Bozhi Lu,Tinglan Yang,Xinyi Zhang,Muxue Wang,Xiaomei Zhang,Hongmei Cao,Daixin Ye

Carbofuran (CBF), which exhibit high toxicity, persistent residues, ease of accumulation, and resistance to degradation, pose serious threats to human health and harm the ecological environment. Therefore, there is an urgent need to develop a rapid and accurate method for detecting CBF. In this work, a low-cost, portable, and easy-to-use paper chip biosensor was developed, integrating smartphones for the detection of CBF pesticide residues. This biosensor facilitates rapid on-site testing, meeting the needs for immediate analysis. CBF has the ability to inhibit acetylcholinesterase (AChE) activity. In the presence of AChE, acetylthiocholine (ATCh) is hydrolyzed to produce thiocholine (TCh). TCh, in turn, can inhibit the catalytic activity of Ni-N-C single-atom nanozymes (SAzyme) synthesized using Ni(OH) 2 nanochip as a metal precursor, which possess high peroxidase activity. Consequently, the concentration of CBF can be determined by observing the resultant color changes. The results showed that this sensor had a good linear response in the range of CBF concentration from 10 to 500 ng/mL, and the LOD was as low as 8.79 ng/mL. In testing three actual samples—Chinese cabbage, cabbage, and lettuce—the recoveries ranged from 81.09% to 125.27%. This demonstrated that the proposed smartphone-based colorimetric paper chip sensor, utilizing Ni-N-C SAzyme, offers an immediate, convenient, and rapid new strategy for detecting CBF.

研究领域: 环境科学 · 分析化学 · 生物传感器 · 食品安全 · 农药检测
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JOURNAL OF STORED PRODUCTS RESEARCH · 2024 · IF 2.7

Insect-resistant activities of Elsholtzia ciliata essential oil and its main components carvone against Tribolium castaneum in different development stages

Junyu Liang,Xiaohan Zhang,Qian Zhang,Yufei Tang,Weibao Kong,Ji Zhang,Yue An

The main objectives of the present study are to introduce a ecologically safe, and natural compound for controlling the red flour beetle , Tribolium castaneum . This study aims to thoroughly examine the effects of Elsholtzia ciliata essential oil ( E. ciliata EO) and its primary components, carvone , on Tribolium castaneum eggs, larvae, pupae, and adults. The study also includes a simulated warehouse test to assess the efficacy of these substances as contact agents, fumigants , repellents, and antifeedants. All of these anti-insect activities were positively correlated with the concentrations of E. ciliata EO and carvone. Firstly, in the contact activity assay, E. ciliata EO and carvone completely inhibited the hatching of eggs and pupae of the T. castaneum at a concentration of 2.5 μL/cm 2 . The LC 50 of E. ciliata EO and carvone were 7.62 and 4.33 μg/adult, respectively, against senior adults (5 weeks old). Secondly, in the fumigant activity assay, 60 mg/L of E. ciliata EO and carvone essentially completely inhibited pupae eclosion . On the other hand, the LD 50 of E. ciliata EO and carvone against senior adults (5 weeks old) were 8.72 and 5.02 mg/L, respectively. Thirdly, for T. castaneum adults, at the highest test concentration, the repellent rate of the E. ciliata EO was above 90%. Fourthly, the larvae and adults of the T. castaneum could reach complete antifeedant activity by E. ciliata EO and carvone at the highest test concentrations. Finally, 3000 ppm of carvone was sufficient to kill all the pests in the warehouse in the simulated warehouse test. In conclusion, the results of this study will contribute to the better control of the storage pest , T. castaneum , and the development of environmentally friendly insecticides based on E. ciliata EO and carvone.

研究领域: 昆虫学 · 植物化学 · 害虫防治
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ANALYTICA CHIMICA ACTA · 2025 · IF 6

Multiple gRNAs-assisted CRISPR/Cas12a-based portable aptasensor enabling glucometer readout for amplification-free and quantitative detection of malathion

Yi Tian,Jiaxuan Chen,Fengzheng Chen,Junru Xu,Lixiang Huang,Liai Peng,Honglei Li,Kai Shi

Background The threat of toxic malathion residues to human health has always been a serious food safety issue. The CRISPR/Cas system represents an innovative detection technology for pesticide residues, but its application to malathion detection has not been reported yet. In addition, the multiple-guide RNA (gRNA) powered-CRISPR/Cas biosensor has the advantages of being fast, sensitive and does not require pre-amplification. However, the reported multiple-gRNA CRISPR/Cas-based biosensors are largely only used for the detection of nucleic acid targets, and there are still certain challenges in detecting non-nucleic acid targets. Results In this work, a multiplex-gRNA-assisted CRISPR/Cas12a-based portable aptasensor (MgCPA) is developed for amplification-free and quantitative detection of malathion using a glucometer. When target malathion is present in the MgCPA strategy, it specifically binds with aptamer and then activates the trans -cleavage activity of the multiplex-gRNA CRISPR/Cas12a. The activated multiple Cas12a/gRNA complexes cut invertase-HP probes on the electrode surface to obtain glucose signals with glucometer assistance. Under optimal conditions, the developed MgCPA strategy achieves satisfactory portable quantitative and sensitive detection of malathion down to 300 fM (S/N = 3) without pre-amplification. Moreover, the satisfactory selectivity, high reproducibility, and good stability of the proposed strategy are also obtained. Due to its excellent and robust shelf life, our developed MgCPA strategy can be practically applied in detecting malathion in orange, apple, cabbage, and spinach samples. Significance Amplification-free, sensitive, portable quantitative and selective detection of malathion in food samples is achieved by employing our developed MgCPA strategy. This strategy not only opens up a new path for the non-nucleic-acid target detection using amplification-free methods based on multiple-gRNA-assisted CRISPR/Cas12a, but also has broad application prospects in ensuring food safety.

研究领域: 生物技术 · 食品安全检测 · 分子诊断
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FOOD CHEMISTRY · 2024 · IF 8.5

Ti3C2 MXene/MoS2@AuNPs ternary nanocomposite for highly sensitive electrochemical detection of phoxim residues in fruits

Jiani Zhang,Xiaohui Guo,Jian Zhang,Xiaobing Guo,Yuying Xu,Lijuan Chen

Phoxim, extensively utilized in agriculture as an organothiophosphate insecticide, has the potential to cause neurotoxicity and pose human health hazards. In this study, an electrochemical enzyme biosensor based on Ti 3 C 2 MXene/MoS 2 @AuNPs/AChE was constructed for the sensitive detection of phoxim. The two-dimensional multilayer structure of Ti 3 C 2 MXene provides a robust framework for MoS 2 , leading to an expansion of the specific surface area and effectively preventing re-stacking of Ti 3 C 2 MXene. Additionally, the synergistic effect of self-reduced grown AuNPs with MoS 2 further improves the electrical conductivity of the composites, while the robust framework provides a favorable microenvironment for immobilization of enzyme molecules. Ti 3 C 2 MXene/MoS 2 @AuNPs electrochemical enzyme sensor showed a significant response to phoxim in the range of 1 × 10 −13  M to 1 × 10 −7  M with a detection limit of 5.29 × 10 −15  M. Moreover, the sensor demonstrated excellent repeatability, reproducibility, and stability, thereby showing its promising potential for real sample detection.

研究领域: 环境科学 · 分析化学
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MICROCHEMICAL JOURNAL · 2026 · IF 5.2

Overcoming the selectivity-stability trade-off: A hydrophobic pillar[6]arene derivative-based electroanalytical strategy for diquat detection

Zan Tan,Fengping Hou,Xiaojing Yang,Li Yang,Nan Dong

Electrochemical detection of diquat (DQ) herbicide residue faces challenges in achieving the trade-off among selectivity, sensitivity, and stability in complex matrices. To overcome this, we reported a supramolecular electrochemical sensor (P6-TATR/AB/GCE) based on a newly synthesized electron-rich, hydrophobic pillar[6]arene-triazatruxene derivative (P6-TATR) integrated with acetylene black (AB). The sensor leverages the high conductivity and electrocatalytic activity of AB, while P6-TATR enables selective DQ recognition through synergistic electrostatic interaction, host-guest complexation, and competitive adsorption. This synergistic combination facilitates rapid DQ reduction at the electrode interface, enabling high-performance DQ monitoring. The proposed sensor demonstrated a low detection limit (0.784 nM), wide linear range (0.001–16.0 μM), and exceptional specificity against 100-fold interfering pesticides and ions. The sensor exhibited excellent reproducibility, with relative standard deviations (RSD) of 2.43% (intra-day), 2.94% (inter-day), and 3.08% (batch-to-batch). It also demonstrated robust long-term stability, retaining 90.4% of its initial signal after 150 days. Practical application in food and environmental samples yielded satisfactory recoveries (80.0%–116.0%) with RSD ≤ 7.4% ( n  = 3), which were corroborated by High Performance Liquid Chromatography (HPLC) validation. The fabricated electrode outperforms existing DQ sensors in selectivity and stability, offering a new strategy for utilizing hydrophobic macrocycles in electrochemical analysis.

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